Nitrogenous polymerization



Patented Jan. 22, 1935 NITROGENOUS PoLYMERr'znTron. I

PROD

Max Albert Kunz, Mannheim, and Karl Koeberle and Erich jBerthold,Ludwigshafen-on-the- Rhine, Germanm assignors to General Aniline Works,Inc., New York, N. Y., a corporation a:

Delaware No Drawing. Application December 4, 1930, Se- 5 I ,iigazlgNo.500,136. In Germany December 11,

"6 Claims. (01. 260-27) The present invention relates to derivatives ofthe hypothetical trihydrocyanic acid and process of producing same.

. Wehave found that. derivatives of the,hypothetical trihydrocyanicacid;

are obtained in excellent yields in a manner readily carried outindustrially by treating cyclic cyanogen compounds, especially; aromaticcarbocyclic and heterocyclic cyanogen compoundswith inorganic acidcondensing agents practically free from water, whereby, when treatingmononuclear cyclic cyanogen compounds, halides must be present. -Acidcondensing agents of the, aforesaid kind are," for example, sulphuricacid,; oleum, chlorosulphonic acid, phosphoric acid, hydro fi halides,aluminium chloride, zinc chloride and phosgene. When polymerizingmononuclear cyanogemcompounds the presence of halides may be ensured byemploying such of the beforementioned condensing agents as arethemselves halides, such. as f or'example chlorosulphonic acid, ormixtures of the said condensing agents comprising such halides, or byadding other-halides, such as alkali metal or, alkaline earth metalhalides, to the beforementio'ned condensing acids. The polymerizationmay'also be carried out in the presence of organic solvents or diluents,the presence of such diluents' being advantageous when eflectingpolymerization by means of acid chlorides. Organic diluents'which may beused are for example benz'ene and its homologues, halogenbenzenes,nitrobenzenes, pyridine and glacial acetic acid. The polymerizationtakes 'placefalready at ordinary temperatures with evolution'of heat.With cyclic cyanogen compounds of the benzene and naphthalene seriespolymerization occurs so violently that it'is advantageous to cool thereaction imixture, whereas with cyanogen compounds of the anthraquinoneseriesthe reac tion mixture may be warmed slightly. Thus for examplewhen para-tolunitrile is intrdou'ced into chlorsulpliomc acid, pure2,4,6 -tri-'para -tolyl- 1,3,5-triazine is obtained in very good yieldswithin a few minutes. When a mixture is homolo gous nitriles isemployed,mixed 2,4,6'-triarylor arylalkyl -1,3,5-triazines areobtained j Thepolymerization products usually obtained in good yields may'bepurifiedby the usual methods it'necessary. ';Th'ey'a're generally speakingsoluble with great difiiculty-in'organic solvents but with comparativeease in concentrated sulphuric I' V. I F: NIV The reaction productsobtainable according to the present invention are partly alreadydyestufis and partly valuable intermediate productstfor I) thepreparation'of'dyestufis. ,7 employed forpharmaceutical purposes, as

They may also be vul-i canization accelerators and the like.

The polymerization products of cyanogen compounds of the anthraquinoneseries and other cyanogen compounds capable of .beingivattedib'ut whichneed have no aflinity for the 'fibres,zusually constitute valuablevatdyestuffs giving powerful dyeings. n a i Thefollowing examples willfurther illustrate the nature of .this invention, but theinvention isnot restricted to these examples. The partsare. by weight... i

Example 1 I 2 parts of benzoni trile. are,.introduced while stirringinto 20 parts of chlorsulphonic acid cooled to 5 below'zerojcentigrade,stirring is continued for a short time at from 0 "to 10 centigrade, thetemperature is allowed to rise to room temperature, stirring iscontinuedfor some time and the reaction mixture is poured onto ice and the2,4,6-triphenyl- 1,3,5-triazine (cyanphenine) which separates in the'form of a white flocculent precipitate is filtered off ,by suctiom, Theyield is practically theoreticalJj The" crudeproduct which correspondsto'the'formula: j

' 1 part of 'para-tolunitrile is introducedalitt-le as at a time into 10parts of chlorsulphonic acid cooled to 10 below zero centigrade, thewhole is kept at the same temperature for half an hour, allowed towarmup slowly to room temperature, diluted. with .5 parts of concentratedsulphuric acid, poured into ice-water, filtered by suction, and thefilter cake washed until neutral and dried. The crude2,4,6-tri-para-tolyl-1,3,5triazine which corresponds to the formula:-

, H] obtained in a yield of about colourless powder .which melts atfrom-274 to 276 C. It crystallizes from glacial acetic acid,

toluene, xylene and nitrobenzene, in which itis.

v N v v CHa 339 M3 obtained in verygoodyields in the form of acolourless powder, melts at'from 1,515 to 148 C; Colourless needlesmelting at from 152 to 153 C. may be obtained therefrom bycrystallization from glacialaceticacid.

' Example 4 2 200 parts of chlorsulphonic acid are cooled to 10 belowzero centigrade while stirring, 6 parts of para-tolunitrile and10.3parts of benzonitrile are slowly introduced, the whole is warmed to from20 to 30- C., kept at this temperature for a short time and worked up inthe usual manner. The resulting polymerization product is a colourlesspowder which melts at from 176 to 178 C. Colourless needles maybeobtained therefrom by crystallization, for example fromglacial aceticacid,

Ezample'5 2;parts' of benzonitrile are dissolvedat5 C; in 2Q ,partsof 12per cent oleum. Dry" hydrogen bromide is led into the solution until asample withdrawn and poured into water deposits a white flocculentprecipitate. The whole is then worked'up. in the usualmanner. Thereaction 'mulay percent is a product obtained is identical with thatobtainable according to Example 1.

Example 6 about zero centigrade and the whole is kept at from 10 to 20.C. for several hours while stirring. The mixture is then diluted withanhydr'ous sulphuric acid, poured into ice-Water and Vfiltered' bysuction. The reaction product obtained which probably corresponds to theforis a colourless powder which rnelts'at about 290 C. and which may beobtained 'in the form of colourless needles by crystallization fromorganic solvents.

Under the said conditions, alpha-naphthonitrile reacts in a similarmanner.

Example 7 parts of 2-amino-3-cyanoanthraquinone' are dissolved in 1250parts of 23'per cent oleuln while stirring and the wholeis heated tofrom 50- to 80 C. As soon as a sa'mplewithdrawn yields orange 'dyei'ngson cotton from an olive brown vat" the whole is allowed to cool and isworked up as described in Example 6. The polymerization product obtainedwhich'p'robably corresponds to the formula:

is an orangepowder which dissolves in concentrated sulphuric acid givingan orange colouration; and which is practically insoluble inalmost all"organic solvents. It maybe purified, when necessary, by dissolutionin'sulphuric acid and dilution of the solution with water or dilutesulphuric acid by way of :the oxonium sulphate which separates as acrystalline precipitate.

The same polymerization product is obtained by treating 2-amino 3-cyanoanthraquinone with hydrochloric acid, acid chlorides, as forexample phosgene,-it being preferable to work in the presence of"diluents and at higher temperatures.

What we claim is:-

1. A- process for the manufacture of nitrogenous polymerizationproducts-which are probably triazine, derivatives, which comprisestr'eating' -a nitrile of a mononuclear carbocyclic compound with asulphuric acid practically free in the presence of a halide.

2. Polymerized homologues of benzonitrile which are probably triazinederivatives, the said polymerization products being difiicultly solublein organic solvents and readily soluble in concentrated sulphuric acid.

3. Polymerized methyl derivatives of benzonitrile which are probablytriazine derivatives, the said polymerization products being diflicultlysoluble in organic solvents from which they crystallize in colourlessneedles, but readily soluble in concentrated sulphuric acid.

4. A process for the manufacture of nitrogenous polymerization productswhich are probably triazine derivatives, which comprises treating anitrile of a carbocyclic compound with an ini'rom water organic acidcondensing agent practically free from water and comprising a halide.

5. A process for the manufacture of nitrogenous polymerization productswhich are probably triazine derivatives, which comprises treating anitrile of a carbocyclic polynuclear compound with a halogen containinginorganic acid condensing agent practically free from water.

6. A process for the manufacture of nitrogenous polymerization productswhich are probably triazine derivatives, which comprises treating anitrile of a carbocyclic polynuclear compound with chlorosulfonic acid.

MAX ALBERT KUNZ. KARL KOEBERLE. ERICH BERTHOLD.

